Spirit soluble yellow dye



United States Patent O" SPIRIT SQLUBLE YELLOW DYE Norman William Fiess, Ringoes, N.J., assignor to American Cyanamid Company, New York, N.Y., a corporation of Maine No Drawing. Appiication December 28, 1956 Serial No. 631,023

6 Claims. (Cl. 260-145) The invention relates to spirit soluble yellow dyes and, more particularly, to the amine salts of the chromium complexes of the coupling of anthranilic acid diazo with a phenyl methyl pyrazolone sulfonic acid, in which at least of the phenyl groups bear 2-chloroor 2,5- chloro-substituents.

The metal complexes (chromium, nickel, copper, cobalt, iron, etc.) of the yellow dyes represented by the formula:

N'-N I on,

N COOH HO N/ where R is an amine salt radical, have been used for imparting yellow color to metal foil, varnishes, plastic materials, inks, and the like. Such use requires a dye which is readily soluble in hydroxylated organic solvents such as ethanol, methanol, 1-3 butylene glycol, polyethylene glycol, diethylene glycol mono ethyl ether, glycerin, sor-bitol, Z-phenoxy ethanol, and hexylene glycol. Although this dye has the required initial solubility in some solvents such as ethanol, there iszextremely poor solution stability so that settling out and'precipitation occurs on standing. This results in a change 'in dye strength as well as a very undesirable insoluble sediment problem.

Chlorinated dyes which difier from the above in having chlorine atoms in the 2-position or in the 2,5-position of the phenyl radical attached directly to the pyrazole ring have shades and solubility properties similar to the unchlorinated dyes and may be used for similar purposes. Furthermore, these chlorinated-dyes in' solution are stable against precipitation and are, therefore, preferred for use in solution. However, the chlorinated dyes bear a higher cost and this higher cost is a distinct disadvantage, which has limited their use.

The present invention shows that dyes derived from coupling anthranilic acid diazo with a, mixture of phenyl- 2,937,165 Patented May 17, 1960 and the solution maintains its stability for long periods In this .way, by the use of the inexpensive unchlorinated material along with only a small proportion of the more expenof time with little or no precipitation of solids.

sive and more difliculty obtainable chloro derivatives, dyes are obtained with solution stability characteristics exhibited by dyes made solely from the more expensive chlorinated coupling components.

It is most surprising that such good results areobtained using such a small proportion of the chloro-coupling components. It might have been expectedythat there would be some advantage to using some of'the chlorocoupling component to improve solution stability, but it is most unusual that by the use of as little as about 5% of the chloro-compound in the mixture, solution stability results about equal to that obtained Using solely the chloro-compound.

Thus, when the unchlorinated component is used alone, up to 50% or more insoluble material forms in a 15 gram per 100 milliliter alcohol solution within 7 days, whereas, when as little as 5 or 10 mols of the chloro derivatives for each 100 mols total of coupling components, is used, negligible amounts of material precipitate out within the same period. j

The dyes are ordinarily made by coupling the diazo of anthranilic acid with the pyrazolone coupling component and then converting to the metal complex and the amine salt.

Various metals are suitable for making the metal complexes such as chromium, nickel, cobalt, copper and iron, but chromium is' preferred.

For preparingthe amine salts, aliphatic and aromatic primary and secondary amines are suitable, and particu- The azo dye is then isolated as a paste and metallized with a metal salt. Although the Zha'lf metal complex has particularly useful properties, sufficient metallizing agent may also be'used'toform a monometallized dye where there is a 1:1 ratio of metal to dye molecule. Addition of the amine in sulfuric acid solution causes precipitation of the amine salts of the metal, complexes.

The. preferred metal complexis the half chromium complex with 20% of the 2,5-dichloro-coupling component and of the nonchlorinated coupling component,in the form of the amine salt using a 50:50 mixture of dicyclohexylam-ine and dibutylamine.

Although it is convenient to couple anthranilicjacid diazo with the mixture of the coupling component s, similar results may also be obtained by mixing the azo dye formed by coupling anthranilic acid diazo with the pyrazolone coupling components separately, and then converting to the metal complex amine salt in which the two dyes are coordinated through the metal, and mixing at the final, as well as at an earlier stage.

The invention is further illustrated by the examples which follow in which parts and percentages are by weight.

EXAMPLE 1 27.5 parts of anthranilic acid are dissolved in 600 parts water with 35 parts hydrochloric acid (20 B.) and diazotized with 34.6 parts sodium nitrite (40%) at 5-10 C. 42.75 parts of 1-(4-sulfophenyl)-3-methyl-5- pyrazolone and 13.55 parts of l-(2,5-dichloro-4-sulfophenyl)-3-methyl-5-pyrazolone are dissolved in 600 parts of water with'69.5 parts caustic (24% solution). 44 parts sodium carbonate (anhydrous) are added and coupling to the diazo is effected at 12 C. The dye is heated to'50" C. and 50 parts sulfuric acid (93%) and 100 parts sodium chloride are added, the mixture is heated to 70 C. and the dye is filtered off.

The dye paste is dissolved in 714 parts water and 15.8

parts anhydrous sodium acetate at 7080 C. and metallized at 98-100 for one hour with a basic chromium acetate solution using suificient to form the half metal complex. The basic chromium acetate solution is prepared by dissolving at C., 38.2 parts Na Cr O .2I-I O in 177 parts water then adding 13.5 parts sulfuric acid (93%), 30.6 parts glacial acetic acid and 12.9 parts Cereloseand then heating at 100 C. for 2 hours. The metallized dye solution is then cooled to C. 1 In a separate container a solution is prepared by dissolving in 362 parts water at room temperature, 29.8 parts dicyclohexylamine and 21.4 parts dibutylamine with 18.5 parts sulfuric acid (93%). The amine solution is added to the dye over a half-hour. The product separates as a light brown precipitate and is filtered oif. If desired, it may be washed with a dilute solution of the amine acid solution to remove impurities. It is dried and ground to a brown powder.

EXAMPLES 2 to 11 The procedure of Example 1 is followed, except that the ratio of 1-(4-sulfophenyl)-3-methyl-5-pyrazolone to 1-(2,5-dichloro-4-sulfophenyl)-3-methyl 5 pyrazolone is varied.

'Similar preparations are carried out with 1-(2-ch1oro- 4-sulfophenyl)-3-methyl-5-pyrazolone.

Preparations are also carried out using mixed alkyl aniline (average molecular weight 168) in place of the dicyclohexyl amine and dibutyl amine.

The proportions used are shown in the table following.

' For comparison, examples are run using the phenylmethylpyrazolone sulfonic acid alone.

Determination of solution stability To approximately 50 milliliters of denatured ethanol is added, with stirring, 7.5 gram of the dye. The mix ture is stirred and held at a temperature of 25 C. for 30 minutes. A small amount of weighed filter aid is added and the mixture is filtered. The amount of insoluble material is determined by weighing the dried filter residue. The stoppered filtrate is then allowed to stand at room temperature for 7 days and any solid material which precipitates is removed by filtration, dried and weighed. The following table shows the amount in percent of material which did not go into solution initially (based on the total dye used), and the amount in percent which separated out'on standing (based on the total dye used), giving an index of the solution stability, based on one series of tests;

In the table are'shown the relative proportions of chlorinated and unchlorinated coupling components and the amine which was used.

TABLE Percent In- Parts soluble in D9 Parts by Coupling natured Alcohol Example Weight Component at Concentra- No. Coupling (Relative Amine tion of 15 g./

Component Molar 100 ml.

Propo)r- Lions Imme- 7 Days diate NO 3 Dicyclohexyl- 2.0 45. 5

amine. NC Dicyclohexyl- 2. 2 32. 6

amino, dibutylamine cquimolar. 18.9 2 64. 7 d 2. 7 0. 3 8: 1.8 0.4 NC=30IIII 2. 2 o. a DG=20 gg ggnu} 1.8 0.4 NG 50::: -do 2. s 0. 3 DO; 10 NG= lMixcd alkyl 3. 3 0. 5

----- DO=6.8- Do=20 iDanililng.

qgzmjtfim NO:7O icyc o exyl- 1. 5 0.3 11 MO=18 Mo :30" i f g gh 1 Run at a concentration of 10 g./l00 ml. 2 Run at a concentration of 20 g./10O ml. 3 NCPheuylmethylpyrazolone sulfonic acid (non-chlorinated). 4 DC-Dichlorophenylmethylpyrazolone sulfonic acid. 5 MOMonocbloropheuylmethylpyrazolone sultonic acid.

I claim: 1. Coordinated metallized azo dyes in the form of their amine salts in which the azo dyes are a mixture of where A is 1,4-phenylene; B is selected from the group consisting of 2,5-dichloro-1,4-phenylene and 2-chloro-1,4- phenylene; and the molar ratio of II to I is between about 1:1 and 1:20.

2. The dyes of claim 1 where the metal is chromium and where the ratio of chromium atoms to azo dye molecules is from 1:1 to 1:2.

3. The dyes of claim 2 where the ratio of metal to azo dye is 1:2. 7

4. The dyes of claim 1 where the amines are dicyclohexylamine and dibutylamine in approximately 50:50 ratio.

5. The dyes of claim 2 where the amines are dicyclohexylamine and dibutylamine in approximately 50:50 ratio.

6.'The dyes of claim 3 where the amines are dicyclohexylaminev and dibutylamine in approximately 50:50 ratio;

References Cited in the file of this patent UNITED STATES PATENTS 2,023,953 Fischer et al Dec. 10, 1935 2,038,298 Kiernan Apr. 21, 1936 2,048,898 Straub et al. July 28, 1936 2,434,173 Mackenzie et a1. Jan. 6, 1948 2,628,960 Freyermuth Feb. 17, 1953 2,826,572 Kuster Mar. 11, 1958 FOREIGN PATENTS 1,117,065 France Feb. 13, 1956 

1. COORDINATED METALLIZED AZO DYES IN THE FORM OF THEIR AMINE SALTS IN WHICH THE AZO DYES ARE A MIXTURE OF 